Preparation of cyclic ether graft copolymers



United States Patent 3,544,659 PREPARATION OF CYCLIC ETHER GRAFT COPOLYMERS Peter A. Schwab, 1601 Trio Lane, and Wayne R. Sorenson, 720 E. Liberty, both of Ponca City, Okla. 74601 No Drawing. Filed Mar. 16, 1967, Ser. No. 623,543 Int. Cl. C08f 29/30 US. Cl. 260-874 8 Claims ABSTRACT OF THE DISCLOSURE A process wherein polyethers are grafted onto a backbone of vinyl polymer containing pendant protonic groups along the backbone. Said process comprises terminating the cationic polymerization of cyclic ethers with the protonic groups of the vinyl polymer.

This invention relates to novel graft copolymers and to a method of preparing them. More particularly, the invention is concerned with grafting a polytetrahydrofuran onto a backbone of a vinyl polymer containing pendant hydroxyl groups positioned along the backbone.

A graft copolymer is comprised of a high molecular weight backbone to which a second polymer is attached at intervals along the chain. A useful route to graft copolymers begins with a polymer containing chemically reactive or functional groups along the chain. These are then sites for the subsequent reactions with monomers or polymers which lead to graft formation. Grafts to copolymeric backbone containing reactive functional groups, such as: hydroxyl, amide, or epoxy groups, along the chain have been reported.

The polymerization of tetrahydrofuran when carried out with many combinations of Lewis acids and strained cyclic ethers (so called promotors), including the boron trifluoride etherateepichlorohydrin system, produces low molecular Weight polymer. High molecular weight polymer can be obtained by polymerizing in the presence of catalysts without cocatalysts or promotors. These include antimony pentachloride, phosphorous pentafluoride, boron trifluoride, triphenylmethyland tropylium salts, and benzenediazonium hexa-fluorophosphate.

Although there are tetrahydrofuran polymers with a variety of end groups, most frequently polytetramethylene ether glycols are obtained; because protonic solvents, such as: methanol or water, are usually employed in terminating the polymerization.

It was unexpectedly discovered that the cationic polymerization of tetrahydrofuran can be terminated with a pendant protonic group of a vinyl polymer backbone with the resulting product being a poly(tetramethylene ether)- vinyl polymer. In this way, the poly(tetrahydrofuran) becomes chemically bonded onto the vinyl polymer. In general, this invention includes tetrahydrofuran and mixtures of tetrahydrofuran with substituted tetrahydrofurans as the substituting grafting monomers. The vinyl polymers included in this invention are those which lend themselves to cationic grafting, that is: any vinyl polymer containing a pendant group which has an active hydrogen. Included among the examples of such vinyl polymers is poly(vinyl chlon'de-c'o-vinyl alcohol-co-vinyl acetate), poly(vinyl chloride-co-vinyl alcohol-co-vinyl neodecanate), poly (styrene-co-hydroxyl-ethyl methacrylate), poly(methyl methacrylate co hydroxylethyl methacrylate, poly(styrene-co-acrylic acid), and poly (vinyl alcohol) The polymerization of tetrahydrofuran using boron tnfluoride etherate and epichlorohydrin as cocatalysts, in the presence of poly(vinyl chloride-co-vinyl alcohol-covinyl acetate) with the percentages of vinyl chloride, vinyl alcohol, vinyl acetate being 91/ 6/ 3, respectively, leads to the formation of poly(tetra-hyd'rofuran) grafted onto the vinyl polymer backbone. I

The vinyl polymer backbone should contain a minimum of about 0.1 percent by weight of hydroxyl containing constituents in order to provide a sufiicient number of active sites along the backbone to give a graft copolymer with the desired properties.

The temperature at which the grafting reaction takes place can vary over fairly wide ranges. A suitable range is 0 C. to 60 C., with the preferred temperature being about 25 C.

The catalysts useful in this invention are Lewis acids.

In addition to the boron trifluoride etherate-epichlorohydrin catalyst system, other catalyst systems Well known in the art can be used. Any compound containing an epoxide group may be used in place of epichlorohydrin. In place of both cocatalysts, antimony pentachloride can be used.

EXAMPLE Polymerization of tetrahydrofuran in the presence of hydroxyl containing poly(vinyl chloride) In a one. pint screw cap resin jar, 25 grams of poly(vinyl chloride-co-vinyl alcohol-co-vinyl acetate) (91/ 6/ 3) is dissolved in milliliters (75 grams) of dry tetrahydrofuran under a nitrogen blanket, at room temperature, giving a slightly viscous solution. Then, 1.0 milliliter (1.25 grams) of boron trifluoride etherate is added and mixed well followed by the addition of 1.0 milliliter (1.18 grams) of epichlorohydrin dropwise. The stirrer is then removed and the jar capped. When the concentration of the solids reaches 40 percent, gelation occurs and the whole solution sets up to a clear, solid mass. This is then precipitated into methanol in a blender. Extraction of the resulting white solid polymer with hot methanol followed by drying in a vacuum oven at 50 C. affords 37 grams of graft copolymer having an of 0.97. Evaporation of the combined methanol washes gave 6.3 grams (15 weight percent) of homo poly(tetrahydrofuran). Any of the before-mentioned catalysts can also be used in place of the boron trifluoride etherate-epichlorohydrin cocatalyst system.

This graft copolymer resembles plasticized poly(vinyl chloride) in that its pressed film is tough and elastomeric. The amount of grafted poly(tetrahydrofuran) can be varied by varying the amount of tetrahydrofuran polymerized. The greater the amount of tetrahydrofuran, the more poly (tetrahydrofuran) grafted. The chain length of molecular weight of the grafted polymer can be varied by changing the concentrations of the cocatalysts. Along with the graft copolymer, there is also formed some ungrafted homo-poly(tetrahydrofuran) which, because it is incompatible with the grafted copolymer, makes the pressed films opaque and cheesy. However, this can easily be removed by extraction with hot methanol.

The mechanical properties of the graft copolymer are also similar to those of plasticized poly(vinyl chloride), as shown in the table. The graft copolymer was formulated with 2.5 phr. of a tin stabilizer, milled and press-polished into sheets from which tensile bars were cut. The tensile strength and percent modulus decreases with increasing grafted poly(tetrahydrofuran) while the percent elongation increases. In a comparison of a 50 phr. graft copolymer and a conventionally plasticized vinyl with 50 phr. dioctyl phthalate, the percent elongation is the same for both samples (350% The low temperature flexibility is about the same for both grafted (50 phr.) and phthalate plasticized (50 phr.) polymers. So also is its susceptibility to mustard staining. The plasticized vinyl mars lacquer because of plasticizer migration; whereas, the grafted copolymer is without effect on a lacquered surface.

4 Since the graft copolymer is an internally plasticized 5. The process of claim 1 wherein the vinyl polymer vinyl resin rather than a resin plasticized with an added is poly(methyl methacrylate-co-hydroxylethyl methacrylow molecular Weight compound, the eflfects of solvent late). are quite different. The graft copolymer (50 phr.) is quite 6. e composition of claim 1 wherein the vinyl polyresistant to trichloroethylene, a dry cleaning solvent, and 1 Selected P the group I1$i$ti1 1g 0f P 1{( Y n-heptane, which would make it very useful for clothing clllonde c0 Y acetate), P y y chlorlde-co- (e.g., coats) and gasoline applications; whereas, the plasvmyl alcohol co vmyl neodecanate), P ticized (50 phr.) vinyl loses most of its plasticizer and hydroxylethyl methacrylata) polylmethyl .methacrylate becomes quite britfle co-hydroxylethyl methacrylate), and,po1y(v1ny1 alcohol).

. 7. The process of claim 1 wherein the Lewis acid and The major advantage of thls graft copolymer Is that epoxrde combination is replaced by antimony pentachloit combines the 100 percent modulus and the low temrid:

perature flexibility of a good monomeric plasticizer with A composition of matter comprising a vinyl po1y the solvent resistance and non-migration of a good polycontaining pendant hydroxyl groups selected f m meric plasticize the group consisting of polyvinyl alcohol and copolymers The following table illustrates the properties of the of a, hydrgxyl containing comonomer having thereon graft copolymers formed by this invention. grafted side groups comprising polymeric tetrahydrofuran.

TABLE.EVALUATION OF GRAFT OOPOLYMERS PREPARED BY THE POLYME RIZATION OF TETRA- 3()THF) IN THE PRESENCE OF POLY(VINYL CHLORIDE-CO-VINYL ALCOHOL-CO-VINYL Pb Phm. cocatalysts 2 P aft d 1 Ely/1)) 100% r. 1- gr 6 p0 y T F Tensile Percent modulus THF 1 BF -0Et 3 ECH 4 poly(THF) 5 extracted vinh (p.s.i.) elong. (p.s.i.)

1 Parts of THF per hundred parts of hydroxy poly(vinyl chloride).

I Parts of cocatalyst per hundred parts of THF.

3 Boron trifluoride etherate.

4 Epichlorohydrin.

5 Parts of grafted poly(1HF) per hundred parts of hydroxy poly(v1 nyl chloride).

0 Percent of ungraited homo-poly(THF) extracted from polymer with hot methanol. 1 0.5 g./100 m1. cyclohexanone at C.

B Propylene oxide used instead of epichlorohydrm.

Polymer not extracted. It is obvious that the invention is not restricted to the References Cit d illustrative example and that it can be practiced in other UNITED STATES PATENTS ways within the scope of the appened claims.

What is claimed is: 9 6/1968 Furukawa 260-67 1. A processfor producing a graft copolymer com- 42,519 7/ 1958 Duggan 260-874 prising polymerizing tetrahydrofuran in the presence of FOREIGN PATENTS an epoxide, a Lewis acid and a vinyl polymer containing pendant hydroxyl groups selected from the group coni ,001,345 8/1965 Great Britain 260-2131 sisting of polyvinyl alcohol and copolymers of a hydroxy containing comonomer at a temperature of 0 to 60 0., OTHER REFERENCES h b polytetrahydrofuran i grafted ont th vinyl Otsu et al.: Graft Polymers Cont. Poyether Chains, J. polymer. '0 Poly. Sci., Pt. 132(2), 223, 6 PP. 1964.

2.. The process of claim 1 wherein a mixture of tetra- 5 hydrofuran and substituted tetrahydrofurans is substituted MURRAY TILLMAN, 'y er for tetrahydrofur-an in step (a). Q L SEOOURO A t arm-m 3. The process of claim 1 wherein the vinyl polymer 8515 an x er is poly(vinyl chloride-co-vinyl alcohol-co-vinyl acetate). CL

, 4. The process of claim 1 wherein the vinyl polymer IS 26 99, 901 poly(styrene-co hydroxylethyl methacrylate). 

